Phthalocyanine dyestuffs



United States Patent The present invention relates to phthalocyaninedyestuffs and to the method for making same.

The phthalocyanine dyestutfs of the present invention may be representedby the formula R e I Z S m Y wherein Z is the radical of aphthalocyanine; Y is a member selected from the group consisting of NH-Os e 2 and FEM].

with m/x molecular proportions of a compound of the formula wherein W isa member selected from the group consisting of -SO Na, -SO K and Z, R,m, n, and m+n are as above defined; and x is the number of amino groupsper molecule of R H o Pyridine or picolines may be used advantageouslyto catalyze the above condensation.

The dyestulf of the present invention may be produced in Bunte salt form(ASO Na or SSO K), or mercapto form (-SH), or disulfide form (--S-S).

3,325,511 Patented June 13, 1967 In the Bunte salt form, the dyes of thepresent invention have the formula and they may be synthesized bycondensing a molecular proportion of F s0201 L Ill LIE-S0313: with mmolecular proportions of wherein Z, R, m, n, and m+n are as abovedefined, and A is a member selected from the group consisting of Na andK. The Bunte salt form of the dyes may be isolated by evaporating todryness the Bunte salt solutions resulting from the condensation step.In preparing the Na Bunte salt, the condensation will be conducted inthe presence of a sodium base, and preparing the K Bunte salt, thecondensation will be conducted in the presence of a potassium base. l

In the mercapto form, the dyes of the pnesent invention have the formulaso -NH@ 2 SH and they may be synthesized by hydrolyzing the above Buntesalt form with acid.

In the disulfide form, the dyes oi the present invention have theformula and they may be synthesized by condensing a molecular proportionof --s Dal-I with m/ x molecular proportions of R R e th 8-5 Thedyestuffs of the present invention have a number of advantages, some ofwhich follow.

The dyestuffs of the present invention are particularly charcterized inthe presence of the above sulfonic acid group. When the sulfonic acidgroups are present in the magnitude above described, the sulfonic acidcontributes to solubility and assists in diffusion of the dye into thefibers, without impairing Wash fastness. Moreover, the sulfonic acidbrightens the dyestulf and contributes blueness to it; this is anespecially important characteristic for phthalocyanine dyes.

The following are specific and non-limiting examples of methodsembodying the present invention. All parts in these examples are byweight unless otherwise specified.

In all of the following examples, CuPc represents the 1 radical ofcopper phthalocyanine; CoPc represents the radical of cobaltphthalocyanine; NiPc represents the radical of nickel phthalocyanine;and Po represents the radical of phthalocyanine.

Example 1 The turquoise dyestuff of the formula may be prepared asfollows.

81.3 parts of are slurried with ice and water at 0 C. to 1,000 parts,and adjusted to pH 5.5-6.0 by adding 20% aqueous Na CO 50.0 parts sodiumS-4-aminophenylthiosulfate and 6.7 parts of pyridine catalyst are addedthereto; the resulting mass is stirred for 23 hours at 0 C. while pH 7.0is

maintained by adding 20% aqueous Na CO as needed, and when pH 7.0 ismaintained at 0 C. without further addition of Na C O the mass isbrought to room temperature during 24 hours, and stirred for anadditional 10 hours at room temperature with addition of Na CO as neededto maintain pH 7.0, thereby permitting condensation.

At this stage the dyestuff exists as a solution of the Bunte salt, andif desired, this solution may be evaporated to dryness and isolated as(The corresponding potassium Bunte salt may be prepared by substitutingan equimolar amount of potassium S-4-aminophenylthiosulfate for thesodium S-4-aminophenylthiosulfate, and KOH or K CO for the Na CO in theabove.)

The above mercapto '(-SH) form of the dyestuff may be prepared byhydrolyzing the above solution of the Bunte 'salt with an acid, such asby adding to the above solution of the Bunte salt enough H 80 to bringthe acid concentration to 7%, heating to reflux during 23 hours, andmaintaining reflux 10 12 hours. The rnercapto form of the dyestuif isisolated by cooling the resulting mass to 50 C., filtering, collectingthe resulting solids, washing the solids acid free with warm water, andoptionally drying the solids or preserving in the moist condition forsubsequent use in preparation of a printing paste.

In the examples given in the following table the procedure is the sameas that given in Example 1, and the examples in the table indicate thata molecular proportion of the phthalocyanine in the second column isreacted with two molecular proportions of the thiosulfate in the thirdcolumn to produce the dye shown by structural formula in the fourthcolumn, having the color shown in 40 the fifth column.

Examples 2-4 lllllx. Phthalocyanine Thiosultate Dye Color 2Sodium-S-(3-amino-5- SH Greenish S O 201 chlorophenyDthiol blue. 1 L 2sulfate. C01 0 \-"SOzNH- O soaH] CoPcL L o 5 Cl 2 I" Potassium S-(Z-SI-I Bluish 3 S 0 01 amino fi-methoxyl green.

L 2 phenyDthiosulfate. NiPc SO1NH OCHa L 2 LS 0 H N1 Po 5 o s 0 3H] rSodium S-(4-arnino-2- CH Turquoise. 4 S O zCl methylphenyl(thiol L asulfate. I" o S Oat-NH SH r L i sonr Fe ES 0 3H] CoPc is 02H] maybeprepared as follows.

This example is the same as Example 1 above, except that 89.8 partsr-smcu] CoI e L M ---SO3H L are substituted for the so 01 L (Julie r soH L a l.

in Example 1, and except that the amount of sodium S-4-aminophenylthiosulfate is increased to 62.5 parts.

Examples 6-8 In the examples given in the following table, the procedureis the same as that given in Example 5, and the examples in the tableindicate that a molecular proportion of the phthalocyanine in the secondcolumn is reacted with 2.5 molecular proportions of the thiosulfate inthe third column to produce the dye shown in the fourth column, havingthe color shown in the fifth column.

6 Example 9 The bluish green dyestuff of the formula s o PNHAHJ a L maybe prepared as follows. This example is the same as Example 1, exceptthat 94.7 parts NiPc are substituted for the SOzCl] C u S 03H] inExample 1, and except that the amount of sodium S-4-aminophenylthiosulfate is increased. to 75.0 parts.

Examples 10-12 112:. Phthaloeyanine Thlosullate Dye Color 6 SodiumS-(3-amlno-4- SH Bluisli green.

S OiCl] bromophenyl) L i 5 thiosulfate. NiPc S 02-NH r Ni Pc 7 PotassiumS-(2- SH Turquoise.

S O 201] amino-sethoxy- L 2 5 phenybthiosuliate. P0 Son-NH OCHnCHa LE LM L S 0 3H P 0 8 I" Sodium S-(4-amino- C H1-C H Turquoise.

S 0101] 3-ethylphcuyl) thio- L 2 5 sulfate. 0 uPc S 01-NI'I SH F L 1.5LS 0 H CuPe I:S 03H] may be prepared as follows.

This example is the same as Example 1 above, except that 89.9 parts113x. Phthaloeyanine Thiosulfate Dye Color 10 r Sodium S-(3-amino- SHTurquoise.

S O a Cl fi-fiuorophenyl) L 3 thiosullate. P F S0q-NH O -SO H L a 1 alie ---s031-1:| 11 l" :1 Potassium S-(Z- SH Turquoise.

S0101 amino--methoxy a phenyl) thiosuliate. CuPG ESO1NH O OCH3 -ESOaH] ciir 3 SO3H] L 12 Sodium S-(4-amino- CH; Turquoise S0101]z-metliylphenyl) 1 blue. 0 P L 3 thiosulfate. so NH SH 0 c 1 LF s ESOgHC0170 SOaH] Example 13 are substituted for the The greenish turquoisedyestufi of the formula I SOzCl F (In e L 2 SO2NH- 0 -SH] L 3.5 soau] TI L 0.5 v TSOSHJOJ in Example 1, and except that the amount of sodiumS-4- aminophenylthiosulfate is increased to 87.5 parts.

Examples 1416 In the examples given in the following table, theprocedure is the same as that given in Example 13, and the F examples inthe table indicate that a molecular propor- SOuCl L 3.5 tron of thephthalocyanine 1n the second column 1s reacted with 3.5 molecularproportions of the thiosulfate i o g] in the third column to produce thedye shown in the L M fourth column, having the shade given in the fifthcolumn.

Ex. Phthalocyanine Thlosulfate Dye Color No.

14 Potassium S-(3- SH Turquoise.

S O 1 Cl] amino-fi-ehloro- E M phenyl) thiosulfate. CuPc SOr-NH- OLEI-803E] SOaI-I] L 0.5 15 Sodium S-(2-amino- SH Turquoise S 01 Cl]fi-ethoxy-phenyl) blue.

3.5 thiosuliate. CoPe -SO1NH@O 011,011;

LL 8031i CoPc sour] 16 Sodium s-( l-amino- CHg-CH: Bluish S O a ClZ-ethyl-phenyl) green. P M thiosullate. SO NH SH Ni 0 S0311 NiPc M soau]9 Example 17 CuPc -Esonr] may be prepared as follows.

58.7 parts of 98.1% copper phthalocyanine are added This example is thesame as Example 17 above, except that instead of evaporating thethiosulfuric acid salt solution to dryness to it are added enoughhydrochloric acid to adjust the acid concentration to 12%, andthereafter the mass is heated evenly to reflux during one hour, andreflux is maintained for 6 hours, thereby converting the dye to themercapto form.

The dyestufi is isolated by cooling the mass to 50 C., filtering,collecting the solids, Washing the solids acid free 10 with warm water,and optionally drying or preserving in evenly during 1 hour to 379 partschlorosulfonic acid the moist condition for subsequent use inpreparation of being stirred at 2040 C.; the temperature is raised duraprinting paste. ing a period of one hour to 135 C. and then maintainedExample 19 at 135140 C. for three additional hours, cooled to 85 Th tblu d t if h f 1 C. during 30 minutes; held at 80-85 C. for one hour 15e urquolse e ys u oft e Ormu a while 49.3 parts 98% thionyl chloride areadded thereto; j stirred three additional hours at 80-85 C.; and cooledto FL J71 room temperature. The mass is drowned in ice Water at J 0 C.,causing precipitation; the precipitate is filtered at TSOaH] [Ho s]- 0C., and washed acid free with water at 0 C.

The dyestuff is isolated by cooling the mass to 50 C., may b re ar d afollow to 840 parts; adjusted to pH 5.56.0by adding 20% aque- 81.3 partsof ous Na CO 63.6 parts sodium S-4-aminopheny1thiosulr fate and 6.7parts pyridine catalyst are added thereto. V-SOzCl] The resulting massis stirred three hours at 0 C. While CuPc L i pH 7.0 is maintained byadding 20% Na CO as needed. F The mass is then warmed evenly during fourhours to J room temperature, and stirred 16 hours at room temperature,whereupon the dye is in the form of a solution are added to a solutionof 37.2 parts 4,4-diaminodiof its thiosulfuric acid salt.phenyldisulfide in 80 0 parts acetone; 50 parts pyridine areThe'thiosulfuric acid salt form of the dye is isolated as added and themass is stirred at room temperature for 16 a dry powder by evaporatingthe condensation mass soluhours, thereby permitting condensation. tionto dryness. The dyestuif is isolated by filtering, collecting thesolids,

Example 18 washing the solids with acetone and drying. The turquoiseblue dyestufr' of the formula Examples 20-22 F 1 In the examples givenin the followin table the proso I\'H -SH e 2 H cedure is the same asthat glven in Example 19, and the examples in the table indicate that amolecular proportion of the phthalocyanine in the second column isreacted L with ,a molecular proportion of the disulfide in the thirdwherein CuPc is the radical of copper phthalocyanine column to producethe dye shown in the fourth column, may be prepared as follows. havingthe color shown in the fifth column.

I13x. Phthalocyanlne Disulfide Dye Color 20 3,3-dia n -5,5-di- 01 01 '1F t-S0261 2 SfiEEhZi ipheuyIdL urquolse CuPc so NH s s N11 0 s 2 CuPo FCuPe ---so H HO s L 3 1015 l: 3 J05 21 I 2,2-diamino -5,5-di- F Bluish SO i C I] methoxydiphenyl- S O2NH NH--O 28 green l L 2 disulfide. NiPc rS S so H e a 1.5

C1136 6 CH3 2 NiPc F NiPc so H H0 s- L a 10.5 3 J06 22 I 4,4dian1in0'2,2-di- F CH3 CH3 Turquoise.

S O 2 Cl methyldiphenyli L disulfide. Pc -soz-Nu- S-S@NHO2S-T' [SOaH] Poa re 4on1] [HO S 1 1 Example 23 The turquoise blue dyestutf of theformula CoPc F ES03H] [HOaS3- may be prepared as follows.

This example is the same as Example 19 above, except that 89.8 parts ofused in Example 19, and except that the amount of 4,4-diaminodiphenyldisulfide is increased to 46.5 parts.

Epcamples 24-26 1 2 Example 27 The bluish green dyestufi of the formulamay be prepared as follows.

This example is the same as Example 19 above, ex-

cept that 94.7 parts of are substituted for the used in Example 19, andexcept that the amount of 4,4'-diaminodiphenyldisulfide is increased to55.8 parts.

Examples 28-30 In the examples given in the following table, theprocedure is the same as that given in Example 27, and the examples inthe table indicate that a molecular proportion of the phthalocyanine inthe second column is reacted with 1.5 molecular proportions of thedisufide in the third column to produce the dye shown in the fourthcolumn, having the color shown in the fifth column.

21. Ihthaloeyanine Disulfide Dye Color 24 r 3,3-diamln04,4- Bluish S O 2C1 dlbromodiphenyl- B r Br green. L. 2 .5 disulfide. I Ni PG S O NH S SNH O S z- 2 $0.11] [1 Jim L Ni Po NiPc SO H] [HOexS L l 252,2-diamino-5,5- Tur noise.

8 0:01 diethoxydiphenyl- S 0 NH NIH-0131 q L 2 .5 disulfide. 1 Fe S S LS0 3H] 0 I l C 2H5 O O O 2H5 2. 5 Po Po SOsH:| [IIOsS L w l 26 I"4,4-diamino-3,3- C Ha-C H; C Iii-CH3 Turquoise.

S 0 :Cl diethyldiphenylo P H disulfide' so NH 0 s s NH 0 s u c ar a I"Jr .5

S 0 H Cu P 0 Cu Fe SOaH] [floss IFx. Phthalocyanine Disulfide Dye Color0. 2s PS as -dtar tn -as' dir Turquoise. F 0! 1 en l L 2 a di sulhd y "CLSOEH I so NH s s @NH 0 s 4T 2 fl IIc Pc SO:lH] [5038 L J 29 ['80 O1]2,2-dtilamin((1 -5,lt1' -di-1 ["80 NH NH O S'] -Turquoise.

H16 0X 1 6 e L 2 3 dlsulfid p Hy 2 CuPc F S s SOaH] CHsO (|)CH3 3 CuPc IuPc LESOQH 11038151 30 F 4,4-diamino-2,2-di- CH3 CH3 Turquoise SOC1]methyldiphenyll blue. 0 I 3 disumde' so NH s s 3 NH 0 s 0 C l 2- :1 j

sour] CoPc CoPc S 03H] [Hoas L l Example 31 are substituted for the IThe greenish tlllqLlOlSe dyestuff of the formu a Jt S 02 I. .1 CuPc 2FESOzNH-S-S@-NHOzS:I-I Pc L M SOQH] [HOQSJJ 5 used in Example 19, andexcept that the amount of L M 4,4-diaminodiphenyldisulfide is increasedto 65.1 parts. may be prepared as follows. Examples 32-34 This exampleis the same as Example 19 above, ex-

p that 899 parts of In the examples given 1n the following table, theprocedure is the same as that given in Example 30, and the -s0 or]examples in the table indicate that a molecular proporf 2 u tion of thephthalocyanine in the second column is reacted PC with 1.75 molecularproportions of the disulfide in the LE third column to produce the dyeshown in the fourth L M column, having the color shown in the fifthcolumn.

113x. Phthalocyanine Disulfide Dye Color 32 3,3-diamino 5,5-di- Cl ClTurquoise.

S O 101] chlorodiphenyldi- I l L 0.0 sulfide. CuPc L 0.0 --s OzNI-I- s-s--NI-I-O ,s

L J3 ,5 Cu P c C uPc [H038 L 0,5 Jolt 33 2,2-diamino-5,5-dir Turquoise SO a Cl ethoxydiphenyl- S O q-NII NH O gS-1 blue. L 0.0 disulfide. 1 tOoPc F s s S 03H] L 0.0

021150 007115 3.5 Go I" c C P0 SOaII] [HOaS L 0.0 J00 344,4-diamino-2,2-di- CHa-C H: C H2GH3 Bluish S O 101 ethyldiphenyl- Igreen. NT L 0.0 disulfide. SO NH O S O s L Jail.

ES 0 H Ni P c NiPc M smH] |:Eo0s V L 0.5 J0 i5 All of the dyes of thepresent invention may be applied halt phthalocyanine, nickelphthalocyanine and phthaloto cotton fabric by padding onto the fabric acomposition cyan'ine; R is a member selected from the groupconsistcomprising parts dye, 945 parts water, and parts ing of hydrogen,halogen, alkoxy having one or two C 60% sodium sulfide, squeezing thefabric to 70% wet 35 atoms, and alkyl having one or two C atoms; In is apick-up based on fabric weight, drying the fabric, steamnumber from2-3.5; n is a number from 0.5-1; and the ing the fabric, passing thefabric into a chemical oxidizing sum of m+n is from 2.5-4. bathcomprising 985 parts water, 7.5 parts sodium di- 2. The dyestuff of theformula chromate, and 7.5 parts glacial acetic acid, scouring and dryingthe fabric. F

The thiosulfuric acid salt forms of the dyes of the YESO1NH- O SSO3NEL]present invention may be applied to cotton fabric by CuPc V padding ontothe fabric a composition comprising 25 F parts thiosulfuric acid saltform of the dye, 825 parts T J water, parts thiourea and 100 parts urea,drying the 5 fabric, passing the fabric for 90 seconds into a curingoven heated to F and Optionally scouring and wherein CuPc is the radicalof copper phthalocyanine.

vl l h af 'i s c liaimed is' Refemnces Cited 1. A dyestuif of theformula 50 V UNITED STATES PATENTS 3,226,395 12/1965 Schimmelschmidt etal. R R 260-3145 SOZJWQ @NILOZS 3,236,860 2/1966 Schultheis et al.260-3145 Z s-s m Z OTHER REFERENCES Belg. Chemical Abstracts, vol. 57(1962) page 16809e.

\SO H] [H0 5 n WALTER A. MODANCE, Primary Examiner. wherein Z is theradical of the phthalocyanine selected from the group consisting ofcopper phthalocy-anine, co- 60 JAMES PATTEN Assistant Examine"

2. THE DYESTUFF OF THE FORMULA